CN103333516A - Preparation method of 1-amino-4-hydroxyl-anthraquinone - Google Patents
Preparation method of 1-amino-4-hydroxyl-anthraquinone Download PDFInfo
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- CN103333516A CN103333516A CN2013102376645A CN201310237664A CN103333516A CN 103333516 A CN103333516 A CN 103333516A CN 2013102376645 A CN2013102376645 A CN 2013102376645A CN 201310237664 A CN201310237664 A CN 201310237664A CN 103333516 A CN103333516 A CN 103333516A
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Abstract
The invention relates to dye synthesis and particularly relates to a preparation method of 1-amino-4-hydroxyl-anthraquinone. The method is characterized in that 1-amino-2-bromo-4-hydroxyl-anthraquinone and 1,2-alkylglycol which are used as raw materials are debrominated under the action of alkali to generate the target product 1-amino-4-hydroxyl-anthraquinone. The method provided by the invention has the advantages of simple process route, good selectivity, high yield, little pollution, simple aftertreatment and the like, conforms to the current trend of green chemical industry and is of great industrial value.
Description
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Technical field:
The present invention relates to the synthetic of a kind of dyestuff, specifically relate to a kind of preparation method of 1-amino-4-hydroxy-anthraquinone.
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Background technology:
1-amino-4-hydroxy-anthraquinone is a kind of dyestuff, also is the important intermediate of other dispersion, reduction and matching stain.Its existing synthetic method mainly contains following several:
1. be raw material and reaction of sodium azide with the 1-nitroanthraquinone, generate target product 1-amino-4-hydroxy-anthraquinone with the strong sulfuric acid response hydrolysis again, this method raw material is easy to get, but need use sodiumazide and a large amount of vitriol oil of high-risk, industrial safety is low, pollutes bigger.
2. be raw material with Tetra hydro Phthalic anhydride and p-aminophenol, the vitriol oil and boric acid are that cyclization reagent carries out the cyclisation hydrolysis and prepares 1-amino-4-hydroxy-anthraquinone, this method technology is succinct, raw material is more cheap relatively, but easily the oxidized yield that causes is lower owing to the easy hydrolysis of Tetra hydro Phthalic anhydride, p-aminophenol, and need a large amount of vitriol oils to cause huge spent acid to pollute, industrial pressure is bigger.
3. be that raw material obtains target product with the ammonia aminolysis with 1,4-quinizarin, though this method route is succinct, reaction preference is lower, and yield is low, and product is difficult to purify.
4. be raw material with 1-amino-2-bromo-4-hydroxyl-anthraquinone or 1-amino-2-chloro-4-hydroxyl-anthraquinone, obtain target product 1-amino-4-hydroxy-anthraquinone through the hydrazine hydrate reduction dehalogenation, this method route is succinct, simple to operate and yield is good, but also need to use comparatively dangerous and the bigger hydrazine hydrate of pollution, industrial pressure is bigger.
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Summary of the invention:
Problem to be solved by this invention is to overcome the defective that above-mentioned prior art exists, and the preparation method of 1-amino-4-hydroxy-anthraquinone that a kind of synthetic route is simple and direct, yield is high, pollution is little and cost is low is provided.
For this reason, the present invention adopts following technical scheme:
A kind of preparation method of 1-amino-4-hydroxy-anthraquinone is characterized in that, may further comprise the steps: 1-amino-2-bromo-4-hydroxyl-anthraquinone and 1,2-alkyl diol, debrominate obtains target product 1-amino-4-hydroxy-anthraquinone in the presence of alkali.
Synthetic route of the present invention is as follows:
The further setting of the present invention is:
Above-mentioned preparation method preferably carries out in the presence of alkali, and described alkali is selected from a kind of of sodium hydroxide, potassium hydroxide, yellow soda ash and salt of wormwood.The mole dosage of alkali is 1～2 times of 1-amino-2-bromo-4-hydroxyl-anthraquinone mole dosage.
Among the above-mentioned preparation method, 1,2-alkyl diol is preferably and adopts ethylene glycol or 1,2-propylene glycol.Its consumption is 2～10 times of 1-amino-2-bromo-4-hydroxyl-anthraquinone weight, and preferred 3-5 doubly.Based on above-mentioned selection, can obtain better yield.
Among the above-mentioned preparation method, preferred 110～140 ℃ of temperature of reaction has considerable influence for yield.
Beneficial effect of the present invention is as follows:
1, with 1-amino-2-bromo-4-hydroxyl-anthraquinone and 1, the debrominate under the alkali effect of 2-alkyl diol obtains target product 1-amino-4-hydroxy-anthraquinone, this operational path is simple and direct, selectivity good, yield is high, it is little to pollute, and advantages such as aftertreatment is simple, meet the trend of current green chemical industry, have industrial value.
2, the present invention is by the selection of raw material, and by repeatedly experiment discovery, in the presence of selection sodium hydroxide, yellow soda ash and salt of wormwood, react, the mole dosage of controlling alkali simultaneously is 1～2 times of 1-amino-2-bromo-4-hydroxyl-anthraquinone mole dosage, the control temperature of reaction is 110～140 ℃, can obtain good yield.
The invention will be further described below in conjunction with embodiment.
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Embodiment:
The instrument and equipment that uses in following examples: nuclear magnetic resonance analyser, mark in the AVANCE DMX II I 400M(TMS, Bruker company); Liquid chromatography, Agilent HPLC1200(U.S. Agilent company).
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Embodiment 1:
31.8 gram 1-amino-2-bromo-4-hydroxyl-anthraquinones (0.1 mole), 13.8 gram salt of wormwood (0.1 mole) and 100 gram ethylene glycol are joined in the 500mL four-hole bottle, mechanical stirring is in 130 ℃ of reactions down, thin-layer chromatography tracking reaction (developping agent: ethyl acetate: sherwood oil=2:1), raw material disappeared in about 2 hours, and reaction finishes.Be cooled to 80 ℃, add 100 milliliters ethanol again in stirring down, cooling is down to about 5 ℃ with ice-water bath at last gradually, filters, and filter cake is dried to such an extent that dark red solid powder 22.4 restrains liquid content 98.2%, yield 92.0% with 100 milliliters of washings.
Product structure is confirmed:
1HNMR(δppm,?400MHz?,?DMSO):?7.263?(d,?1H,?J=9.6Hz,?H1);?7.352(d,?1H,?J=9.6Hz,?H2);?7.866(dt,?J=1.2Hz,?J=7.6Hz,?1H,?H4);?7.927(dt,?J=1.2Hz,?J=7.6Hz,?2H,?H5);?8.240(d,?1H,?J=7.6Hz,?H3);?8.243(d,?1H,?J=7.6Hz,?H6)。
13CNMR(δppm,100MHz,?DMSO):?186.86;?181.37;?161.17;?148.10;?135.03;?134.86;?133.26;?132.56;?130.75;?128.57;?126.70;?126.33;?112.83;?107.22。
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Embodiment 2:
With 31.8 gram 1-amino-2-bromo-4-hydroxyl-anthraquinones (0.1 mole), 8.4 gram potassium hydroxide (0.15 mole) and 150 grams 1, the 2-propylene glycol joins in the 500mL four-hole bottle, mechanical stirring is in 140 ℃ of reactions down, thin-layer chromatography tracking reaction (developping agent: ethyl acetate: sherwood oil=2:1), raw material disappeared in about 2 hours, and reaction finishes.Be cooled to 60 ℃, add 100 milliliters methyl alcohol again in stirring down, cooling is down to about 5 ℃ with ice-water bath at last gradually, filters, and filter cake is dried to such an extent that dark red solid powder 21.3 restrains liquid content 98.4%, yield 87.7% with 100 milliliters of washings.
The product nuclear magnetic spectrogram is identical with embodiment 1.
Embodiment 3:
31.8 gram 1-amino-2-bromo-4-hydroxyl-anthraquinones (0.1 mole), 8.0 gram sodium hydroxide (0.2 mole) and 80 gram ethylene glycol are joined in the 500mL four-hole bottle, mechanical stirring is in 120 ℃ of reactions down, thin-layer chromatography tracking reaction (developping agent: ethyl acetate: sherwood oil=2:1), raw material disappeared in about 2 hours, and reaction finishes.Be cooled to 80 ℃, in stirring the ethanol that adds 100 milliliters down, cooling is down to about 5 ℃ with ice-water bath at last gradually, filters, and adds 100 milliliters of washings again, oven dry dark red solid powder 21.7 grams, liquid content 97.5%, yield 88.5%.
The product nuclear magnetic spectrogram is identical with embodiment 1.
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Embodiment 4:
With 31.8 gram 1-amino-2-bromo-4-hydroxyl-anthraquinones (0.1 mole), 12.7 gram yellow soda ash (0.12 mole) and 200 grams 1, the 2-propylene glycol joins in the 500mL four-hole bottle, mechanical stirring is in 110 ℃ of reactions down, thin-layer chromatography tracking reaction (developping agent: ethyl acetate: sherwood oil=2:1), raw material disappeared in about 2 hours, and reaction finishes.Be cooled to 60 ℃, add 100 milliliters methyl alcohol again in stirring down, cooling is down to about 5 ℃ with ice-water bath at last gradually, filters, and adds 100 milliliters of washings, dries to such an extent that dark red solid powder 20.7 restrains liquid content 98.6%, yield 85.4%.
The product nuclear magnetic spectrogram is identical with embodiment 1.
What need statement is that foregoing invention content and embodiment are intended to prove the practical application of technical scheme provided by the present invention, should not be construed as the restriction to protection domain of the present invention.
Claims (7)
1. the preparation method of a 1-amino-4-hydroxy-anthraquinone is characterized in that, may further comprise the steps: be raw material with 1-amino-2-bromo-4-hydroxyl-anthraquinone and 1,2-alkyl diol, debrominate obtains 1-amino-4-hydroxy-anthraquinone under the effect of alkali.
2. the preparation method of a kind of 1-amino-4-hydroxy-anthraquinone according to claim 1, it is characterized in that: described alkali is selected from a kind of of sodium hydroxide, potassium hydroxide, yellow soda ash and salt of wormwood.
3. the preparation method of a kind of 1-amino-4-hydroxy-anthraquinone according to claim 1 and 2, it is characterized in that: described alkali mole dosage is 1～2 times of 1-amino-2-bromo-4-hydroxyl-anthraquinone mole dosage.
4. the preparation method of a kind of 1-amino-4-hydroxy-anthraquinone according to claim 1 is characterized in that: described 1, the 2-alkyl diol is ethylene glycol or 1,2-propylene glycol.
5. the preparation method of a kind of 1-amino-4-hydroxy-anthraquinone according to claim 1 and 2 is characterized in that: described 1,2-alkyl diol consumption is 2～10 times of 1-amino-2-bromo-4-hydroxyl-anthraquinone weight.
6. the preparation method of a kind of 1-amino-4-hydroxy-anthraquinone according to claim 5 is characterized in that: described 1,2-alkyl diol consumption be 1-amino-2-bromo-4-hydroxyl-anthraquinone weight 3-5 doubly.
7. the preparation method of a kind of 1-amino-4-hydroxy-anthraquinone according to claim 1, it is characterized in that: described debromination temperature is 110～140 ℃.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1043929A (en) * | 1988-12-27 | 1990-07-18 | 伊斯曼柯达公司 | The method of dehydrohalogenating aromatic halides |
| CN101348420A (en) * | 2008-09-12 | 2009-01-21 | 湖南利洁生物化工有限公司 | Hydrogenation dehalogenation method of halogenated alkyl phenol coumpound |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1043929A (en) * | 1988-12-27 | 1990-07-18 | 伊斯曼柯达公司 | The method of dehydrohalogenating aromatic halides |
| CN101348420A (en) * | 2008-09-12 | 2009-01-21 | 湖南利洁生物化工有限公司 | Hydrogenation dehalogenation method of halogenated alkyl phenol coumpound |
Non-Patent Citations (1)
| Title |
|---|
| 杨希川等: "1-氨基-2-溴-4-羟基蒽醌合成新工艺研究", 《大连理工大学学报》, no. 03, 30 May 2000 (2000-05-30) * |
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